Esters of thiophene-modified maleic anhydride-styrene copolymers



Patented Oct. 6, 1953 IESTERiS -'-OF"T-HIOBHENEMODIFIED MALEIC ANH YDRIDE-STY RENE COPOLYMERS Eerdinandll 10th) Company, Inch York "No Drawing.

129, 19:49, ISerial 'No.

- :Mmlication June 27,

and Orland Reiflf, Woodrburry :N. J" .assien rs to ,Sncony-Macuum .0111

Original unrated, 5a gcorporalticnnf New application {September 37.08. .hividlfdzandthk 51, bsellialrNoxzza irafi -1 This invention relates generally to .improyed ilubricating oil compositions. M0176 particularly, --itrelatesto lubricating oil compositions containing EQSQQITS of vthliophenei-nnodified, rmaleic an- .thysiriderstyrene copolymersiaszppur:pointsdepresrsazntszand viscosity:indexzimprovers.

In a .cQpending :application, Serial 'ZN0."H36}1"06, filed March :20, 21941, mow iPatent'lNo. "255703846, :patentedzQctobenQ, 1 951, byith and Robert W. 'LBarrett, 1 lubricating =tions containing rcopolymers :of :styrene andma- :Jeic anhydride, .=;esterified w'ith aliphatic alcohols having .from about '210 ito a-bout -l'8 carbon 'atoms :as V. CE. :improvers and pour pointdepressants'aa e disclosed and :claimed.

As is well known, mineral lubricating 'oils'tend to decompose, especiallymnder heat and oxidizing conditions, such as those encounteredin .use in internal combusticnengines. The decomposition products formed in the 'oil are acidic in nature and exert a corrosive :action-upon the metal surjfaces dosing lubricated.

We, have now .found that when styrene -:is coxpplymerized with maleicanhydride the presoil compovs'ihence. ofithiophene, or. alkylathiophenes,ithiophenetype ,sulfur ,is introduced into .the ,copolymer molecule. We haveyfcund .fur'ther that the sul- ;fur-containing Polymer ,products may then be esterified with primary, normaLsaturated alcojhols having. from about {-10 .to about .18 carbon atoms, .to provide products, which are not-only ,efiective viscosity index:improyers;and pour point depressants .for lubricating ,oils, but which are also efiective antioxidants in ,lubricating oils.

2 Thus, these ester products =inhibit ;the tendency I of such oils to decompose ,in ,use .andrthereby re- '*tard-,.the normal corrosiveefiects exerted byithe oil on-the metalsurfacesbeing.lubricated.

It is the primary .object of this invention to provide improved lubricating oil compositions containing the thiophen'e' mo'dified, styrene-ma- ,leic anhydride esters-herein contemplated. v:Qther golgj ects will, become apparent ;:from *cWhBii; follows.

As far as isknown.theresterifiedzthiophenemodified styreneemaleic .anhydride copolymers have not been known heretofore, and they, .ar.e, therefore, contemplated herein 'as "new compositions of matter.

"The thiophene compounds suitable for us in preparing the pOlymenproductsof the invention may be represented' by-the' general formula e present inventors .wheraRL. and R renresentihydnq enlor alkyl groups, which may be straight, branchchained or cycloaliphatic, in structure. As typical examples of suitablethiop'hene compounds, there may be :mentioned rthiophene per -.2-amethy1 thiophene, 3-methyl thiopl ene, Z-tertiary-butyl thiophene, 2,5ediatertiaryebutylthiophene, 2,3,5- .trimethyl thiophene, 2,3,4,5-tetra-methyl thiog ph ne. 2,5-dimethyl, 3,4-dietl yl :thiophene, 32- ;cyclohexyl thiophene, 2-dodecyl thiophene, :2- !octadecyl thiophene, 2-wax thiophene randj2ifi- ;di-Wax thiophene.

The esterified thiopheneemodified copolymer products -cif1.the invention "are prepared by, "first, reacting together maleic anhydride and styrene :the presence of the thiqphene derivative to :form the thiophene modified, maleic anhydri'destyrenecopolymerandthen esterifying :theprodnot :with the alcohol.

, Substantially.equimolar .;quantities of 'maleic 'anhydride and styrene are employed in the copolymerization reactiomthethiophenecompound being present in at leastaboutequimolar amount, and preferably in excess, the preferred amount being :from 53130111114 frto about s-1'0 moles per "mole of maleic anhydridegonstyrenaisince these latter amounts provideproducts havingmhe largest per- .centages of ,thiophene incorporated therein.

The reaction may also -be carried out with the ,aid of benzene, xylene, dioxane-or 'the'jlike as solvent vmaterials where desirable.

Suitable reaction temperatures range from about 75 :C'.--toa'bout =1 25 C., -the :normal practice fbeing to :utilize a temperature sufiicient to maintainthe reaction mixture at gentle reflux. The time of reaction varies between about =-1 Midas-bout 1'0 hoursghowever, the reaction is generally comzpleted-in from a-bout 2 to- -abou't '7 hours.

We have ound thab-a catalys't t is unnecessary, although the reaotion -is facilitated by the-use of a --'smal1amount,'=from about -1 to 5*weight--per--cent, based on the amount'of male'ic anhydr ide used, of an *organic "peroxide -catalyst, such *as -benzoyl peroxide.

=tliiophene-modifled copolymer product is esterified with aprimaty..norma1, saturated, aliphatic alcohol to *produce-theesterified copolymers .;of $11.6 invention. 'whe aestefification ir action is effected under iordincrt t fi t conditions, i. ebyheating,thecopolymer and the alcohol in the presence of strong sulfuric acid.

The saturated, normal alcohols suitable for providing the "products 'herein contemplated are it-hose :having from about "10 to -about"1-8 carbon 'atoms. *Any of these alcohols "Will yield ester products which are effective as V. I. improvers in mineral oils. However, only those relatively pure alcohols having from 14 to 16 carbon atoms, or a mixture of alcohols having an average of about 14 carbon atoms, willprovide products which are effective as pour point depressants.

Specifically, the alcohols which we may use are decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl alcohols. A preferred alcohol reactant, however, is Lorol-B. This is a mixture of alcohols marketed by E. I. du Pont de Nemours 8: Company, which contains saturated, straight-chain alcohols in the following approximate proportions; 2.5% of C-10 alcohols, 55.0% of C-12 alcohols, 20.5% of C-14 alcohols, 9.0% of -16 alcohols and 13.0% of C-18 alcohols; the average chain length of the alcohols being 13.5 carbon atoms per molecule.

A more complete understanding of the invention will be had from the following examples illustrating detailed procedures which may be conveniently followed in preparing our new reaction products.

EXAMPLE I Thiophene-modified styrene-maleic anhydride copolymer REACTION MIXTURE Grams Maleic anhydride 24.5 Styrene 25.5 Thiophene 200.0 Benzoyl peroxide 1.0

These reactants were placed in a /2 liter stainless steel stirring-type autoclave. The autoclave temperature was maintained at 121 C. for a period of 6 /2 hours. The product, a brittle, thiophene-insolu-ble material, was then isolated by filtration and dissolved in acetone. By pouring this solution into methanol, filtering and drying the precipitate, there was obtained 3'7 grams of a pale brown, amorphous powder containing 2.1% sulfur.

EXAMPLE II 2-methylthiophene-modified styrene-maleic anhydride copolymer REACTION MIXTURE Maleic anhydride grams 49 Styrene do 40 2-methylthiophene cc 500 Benzoyl peroxide gram 1.0

These reactants were placed in a 3-neck, roundbottom flask equipped with a reflux condenser, thermometer and mechanically driven stirrer. The mixture was then refluxed for a period of hours at 116 C. The product, an amorphous, pale brown, insoluble material, was isolated from the solvent layer by decantation, and then dissolved in acetone. By pouring this solution into methanol, filtering and drying the precipitate, there was obtained 53 grams of a pale brown, amorphous powder containing 3.3% sulfur. A saponification value of 537 indicated that the product contains 47% by weight of maleic anhydride.

EXAMPLE III 3-methylthiophene-modifled styrene-maleic anhydride copolymer REACTION MIXTURE Maleic anhydride grams... 49 Styrene do 50 3-methylthiophene cc. 500

. dissolved in acetone.

These reactants were placed in a 3-neck, roundbottom flask equipped with a reflux condenser, thermometer and mechanically driven stirrer. The mixture was then heated for a period of 5 hours at 119" C. The product, an amorphous,

pale brown, insoluble material, was isolated from the solvent layer by decantation and then dissolved in acetone. By pouring this solution into methanol, filtering 1 and drying the precipitate, there was obtained 84 grams of a pale brown, amorphous, powder containing 4.8% sulfur. A saponification value of 519 indicated that the product contains 45.3% by weight maleic anhydride.

EXAMPLE IV 2-t-butyZthiophene-modified styrene-mulch:

- anhydride copolymer I REACTION MIXTURE Maleic anhydride grams. 49 Styrene do 52 2-t.-butylthiophene cc 250 Benzoyl peroxide gram 1.0

These reactants were placed in a 3-neck, roundbottom flask equipped with a reflux condenser, thermometer and mechanically driven stirrer. The mixture was then heated for a period of 2 hours at 90 C. The product, a brittle, insoluble material, was then isolated by filtration and By pouring this solution into methanol, filtering and drying the precipitate, there was obtained 79.5 grams of 'a pale brown, amorphous powder containing 2.1% sulfur. A saponification value of 531 indicated that the product contains 46.5% by weight maleic anhydride.

EXAMPLE V v 2,5-di-t-butylthiophene-modified styrene-maleic anhydride copolymer REACTION MIXTURE Maleic anhydride gram 49 Styrene do 52 Benzoyl peroxide gram 1.0 2,5-di-t-butylthiophene cc 250 These reactants were placedin a 3-neck, roundbottom flask equipped with a reflux condenser, thermometer and mechanically driven stirrer. The mixture was then heated to 80 C. and as the result of a violently exothermic reaction the temperature rose to 180 C. The product, a brittle insoluble material, was then isolated by decantation and dissolved in acetone. By pouring this solution into methanol, filtering and drying the precipitate, there was obtained 82 grams of a pale brown, amorphous powder containing 1.66% sulfur. A saponification value of 495 indicated that the product contains 43.2% by weight of maleic anhydride.

EXAMPLE VI S-methyZthiophene-modified styrene-maleic cmhydrz'de copolymer (xylene solvent and a mol. equivalent of 3-methylthiophene REACTION MIXTURE Maleic anhydride 49 grams (/2 mole). Styrene 52 grams A2 mole). B-methylthiophene 49 grams /2 mole). Benzoyl peroxide 1.0 gram. Xylene 600 cc.

The reactants were placed in a 3-neck, roundbottom flask equipped with a reflux condenser, thermometer and mechanically driven stirrer.

e z yl p r id "gram" 1,0, The mixture was then heated to C. and as esteem 5 a result of an exothermic reaction, the tempera- .turezroseito 21140 .C. .After cooling .139 -1Il5.C .the .mixture was maintained at this {temperature-for onehour. The product, an almost white, xyleneinsoluble, amorphoussolid, was filtered from the reaction solvehtioy 'means'nf aBuchner funnel. Further purification was accomplished b y dissolving the polymer in acetone 16300 ce.) andpouring this-solution into methanol (1500 c). The pre cipitated product, after separation '-'and :drying, was a white, amorphous powder weighing 19 grams and containing 0.319 ssulfur.

VII Styrcne-mdteic anhydrzd-e copolymer :(nylene solvent) REACTION MIXTURE Maleic anhydrid'e grams Styrene t -52 Xylene 600 Benzoyl zperoxide gram 1.0

The reactants "were placed in 'a s-ne'ck, round- :bottom flask equipped with a reflux condenser, a thermometer and a mechanically driven stir- :rer. The :mixture was :then .heated for a meriod of .on'e'j'hourat 1'10-:12'D IC. The :product, a white, amorphoussolid, was isolated by filtration {and Washed with xylene and methanol. After oven dnyingfithe ipo'lymer weighed 100 grams.

:Di "iL-o'n'ol'e'B :ester :of the .thiophene moliz'fi'ed rstynen'e-maleic anhydride-copolymer of Example?! REACTION MIXTURE "I'hiophene m'odifi'ed styrene-male'ic anhy- 'dride 'co'polymer -(Ex. 'I) grams 115.1) "Lorol-B -iio .4'010 Xylene cc .200 Sulfuric acid (98 t. cc 7013 The reaction :mixture was :placed in a nneliter, three-neck flask equippediwith:aathermometer, m'echanical stirrer and condenser. Between :the :condenser and flask was placed .a Dean rand Stark moisture trap :fittted with :a :stopc'cck for removing water and solvent when so desire'd. .A short While after the mixture had :been heated -at Ithe ireflux temperature of IMO-I150 1 0., :the .suspended vcopcilymer :gradually :reacted -:.to :form the half Tester. I he :homogeneous solution ?thus *obtained was then :maintained at this temperraturefor about 3 hours, during which time ithe water :,of reaction :-;slowly :idistilled .over into :the moisture trap, with the :aid @of the refluxing xylene solvent. The ;-xylene was then permitted to distill oif until zthe :temperature =r If (the ireaction mixture had reached 160 C. After utemaining for about minutes at this temperature, the product was permitted to cool to room temperature. The viscous composition was then diluted with 100 cc. of benzol and stirred .with about 10 grams of sodium bicarbonate .to neutralize the .acidic catalyst. After filtration through I-Ii-fFlo clay, ":lJhB lfiltrate was topped to 300 C. at 5 mm. pressure to remove :solvents and ,unreacted Lorol alcohol. The product, a light brown, tacky 'material, had a neutralization number of 6.0, .indicatingthat essentially complete esteriflcation of the lnopolymer -had ;,product was "0.82%. r

The "product'o'f Example VIII wasjfree 61 mineral oil in thefinished form. .Someroftheproducts in the following examples were blended with 75 Sulfuric acid (98%) cc taken place. "The sulfur content df the finished 7 B mineml roil to the extent .of "to the viscosity of the additive and' thus facilitate .iur ther blending operations. All concentrations of the various esters evaluated are, however, reported on thebasisof mineral .,oil-free products.

Di "LoroZ-B ester of .the v.2-methylthiop henemodified styrene mdlic anihydrz'de copolymer of Example II 'REA'CTIUN'MTXTURE 2smethyltliiophene-modified styrene-maleic ;an'hy'dride copo'lymer '(ExarnpleII grams ISL'O "1.01 6148" -'do.. 137.5 Xylene Icc.. 200 Sulfuric acid (98%) cc 0.3

was followed as .grams. 1520 moro1-;B.. .'-.do 5.33125 Xylene cc 200 Sulfuric acid (98%) cc 0.3

.Ihe .same {general .procedure was followed outlined..in Example VIII.

EXAMPLE XI Di LoroL-B;estcr 0f rifle- 2wt butylthiophenemodified styrene-maleic .anhydride .copolymer of Example TIV REACTION MIXTURE .2 t-butylthiophene-modified styreneemaleic ianhydride copolymer (Example IV) Di LoroZ-B ester of the 2,5-t-butylthi'ophenemodified 'styrene-mdle'ic "mihy'dfid'e 0017011177187 of Eramfite v REACTION MIXTURE '25-di-t -"-butylth'iophene modified styrene- "maleic 'anhydride copolym'er (Example V) grams 15;0 Lorol-B do 37.5 Xylene cc 100 Sulfuric acid (98%) cc 0.3

The same general procedure was followed as outlined in Example VIII.

4 EXAMPLE XIII "Di "Eo'rdl B ester of 3-methylthiophenemodified styrene-malez'c anhydride corpolymer ofli'mampleyl REACTION .MIXHJURE fl-methylthiophene modified 'styrene-maleic antrydri'def'copolymerIExan ple VI) I I grams 15.0 Enrol-1B s d0 37.5 Xylene cc 200 0.3

The same general procedure was followed as outlined in Example VIII.

EXAMPLE XIV Di Lorol-B esterof the styrene-maleic anhydride copolymer of Example VII REACTION MIXTURE V Styrene-maleic anhydride copolymer (Ex ample VII) grams 15.0 "Lorol-B do 37.5 Xylene cc 200 Sulfuric acid (98%) cc 0.3

The same general procedure was followed as outlined in Example VIII.

XV-A

Di-decyl ester of the 3-methyZthiophene-modified styrene-maleio anhydride copolymer of Example VI REACTION MIXTURE EXAMPLE XV-B Didodecyl ester of the 3-methylthiophene-modifled styrenemaleic anhydride copolymer of Example VI V REACTION MIXTURE 3-methy1thiophene-modified styrene-maleic anhydride copolymer (Example VI) grams 15.0 l-dodecanol do 33.0 Xylene cc 200 Sulfuric acid (98%) cc 0.5

EXAMPLE XV-C Di-tetradecyl ester of the 3-methylthiophenemodified styrene-maleic anhydride copolymer of Example VI REACTION MIXTURE 3-methylthiophene-modified styrene-maleic EXAMPLE XV-D Di-hexadecyl ester of the 3-methylthiophenemodified styrene-maleic anhydride copolymer of Example VI REACTION MIXTURE 3-methylthiophene-modified styrene-maleic EXAMPLE XV.E

Di-octadecyl ester of the '3-methylthiophenemodified styrene-male'ic anhydride copolymer of Example VI REACTION MIXTURE 3-methylthiophene-modified styrene-maleic anhydride copolymer (Example VI) grams 15.0 l-octadecanol do-.. 46.0 Xylene cc 200 Sulfuric acid (98%) cc 1.0

The same general procedure was followed for these products as outlined in Example VIII.

Pour point depression and V. I. improvement To demonstrate the eifectiveness of the various products in reducing the pour point and increasing the viscosity index of lubricating oils, the results obtained in tests conducted on blends of the various products in various proportions in lubricating oils are presented in Tables I and II.

Two different base oils were used in these tests, Oil A being a solvent-refined Mid-Continent, SAE 30 grade oil having a kinematic viscosity at 210 F. of 11.96 and a 20 F. pour point, and Oil B being an acid-refined, Mid-Continent stock with a kinematic viscosity at 100 F. of 30.49, a kinematic viscosity at 210 F. of 4.83 and a viscosity index of 80.1.

Table I shows the effect of varying the type of thiophene derivative utilized in modifying the styrene-maleic anhydride copolymer, while Table II shows the effect of varying the ester chain length of the 3-methylthiophene-modified copolymer. It will be observed from Table I that the best results were obtained with the copolymers modified with the branched-chain alkyl thiophene derivatives, while Table II shows that only the esters derived from the 14 and. 16 carbon an y copolymer (Example VI) atom alcohols to be efiective as pour point depressants, although good viscosity index imp-rovel-tetradecanol d0 ment is effected by the esters of any of the alco- Xylene cc 200 hols having from 10 carbon atoms up to 18 carbon Sulfuric acid (98%) cc 0.3 atoms.

TABLE I ASTM Pour V. I. of 1% Blend in PointinOilA OilB Ex. No. Thiophene Compound Type Ester v L Kin.Vis. Kin. Vis. 54% 34% @100" F. @210 F.

111 Thiophene Lor01-B-- 30 20 +15 31.94 5.01 3, 1X 2-Methylthiophene do 30 -25 -l0 32.97 5.18 3-Methy1th1ophenedo -20 l5 +5 32.42 5.09 89.2 2-t-B uty1tl1lophene do 30 30 25 35.69 5.60 104.4 2 5.d -i;-But y1thiophene do 30 30 -25 39.52 6. 23 114.8 s-Methylthiopene (Molecular .....d0 30 -25 33.34 5.25 95.5

Equlvalent+Xylene) ers? Thiophene campsite Fceoowwco' 'JPE NQAN ducted on blends of the anouls tit uots in a solvent-refined'oil hja kinematic viscosity of 8.2at 210 l t, are'given in 'Iable III. As can be observed"froni' tlie dataj the product of Example XIV, which was not modified with a thiophene compound, does not prevent bearing corrosion, whereas the thiophene-modified products provide substantial corrosion inhibition.

iio b t spectslxsuchsafs eiitreme' pr e'ssure quality} det'ergency; eitcL.

Although; the principlsi of the invention have been" illustratedliereinsby means of. certainspecific examples and tests, it is'; not. intended that the scope ofthe" inventidn be limited thereby, ""th igs? 1 49'; e 17,19 2;

(b), about, 1 moleof 125 C'.,and'- (2) enfy'in'g"the product ob't' in step (1) with a primary,

normal, saturated alcohol having from about 10 to about 18 carbon atoms.

2. As a new composition of matter, a reaction TABLE III Bearing Wt. Loss m s.) in gugobga Tee: glD-G dBear- Product of g oncen ra one A ditive ample N 0. Product 2% 1% m gfi VIII Di Lorol-B" Ester of the Thiophene 14 5 20 Modified Styrene-Maleic Anhydride Copolymer. X Di Lorol-B" Ester of the 3-Methy1thio- 0 1 phene Modified Styrene-Maleic Anhydride Copolymer. XI Di Lorol-B" Ester of the l-t-Butylthio- 4 6 24 hene Modified Styrene-Maleic Anhylde Copolymer. XIV Di "Lorol-B Ester of the Styrene-Maleic 24 34 18 Anhydride Oopolymer.

Although, as demonstrated herein, oils containing of the products of the invention are markedly improved, significant improvement will be obtained by the use of as little as .01%. Furthermore, although amounts up to about 1% are generally sufiicient, in certain applications as much as 10% of the additive compounds are used. Also, it is contemplated that the products of the invention be incorporated in greater concentration, i. e. above 10%. to provide "concentrates of these materials in oil for marketing, such concentrated compositions affording a readily soluble form of the additive materials for dilution with further quantities of oil prior to actual use.

The oils in which our new addition agents are incorporated, or the oil concentrates, may also contain other addition agents, designed to improve the character of the oil in other reproduct prepared by the steps of (1) reacting together (a) about 1 mole of maleic anhydride, (b) about 1 mole of styrene and (c) from about 1 to about 10 moles of a thiophene compound selected from the group consisting of thiophene and alkyl-substituted thiophenes containing no substituent groups other than alkyl groups, at a temperature of from about 75 C. to about C., and (2) esterifying the product thus ob tained with a mixture of prima normal, saturated alcohols having an average of about 14 carbon atoms per molecule.

3. As a new composition of matter, a reaction product prepared by the steps of (1) reacting together (a) about 1 mole of maleic anhydride, (b) about 1 mole of styrene and (c) from about 1 to about 10 moles of 2-tertiary-butyl thiophene and (2) esterifying the product obtained in step (1) with a primary, normal, saturated 4. As a new composition of matter, a reactions product prepared by the steps of' (1) reactingtogether (a) about 1 mole 1 to about 10 moles of 2-tertiary-butyl thiophene and (2) esterifying the product obtained in step (1) witha mixture of primary, normal,

saturated alcohols having an average of about 14 carbon atoms per molecule.

5. As a new composition of matter, a reaction product prepared by the steps of (1) reacting together (a) about 1 mole of maleic anhydride, (1)) about 1 mole of styrene and (c) from about 1 to about 10 moles of Z-methyl thiophene and (2) esterifying the product obtained in step (1) with a primary, normal, saturated alcohol having from about 10 to about 18 carbon atoms.

6. As a new composition of matter, a reaction product prepared by the steps of 1) reacting together (a) about 1 mole of maleic anhydride, (1)) about 1 mole of styrene and (c) from about 1 to about 10 moles of Z-methyl thiophene and (2) esterifying the product obtained instep (1) with a mixture of primary, normal, saturated alcohols having an average of about 14 carbon atoms per molecule.

'7. As a new composition of matter, a reaction product prepared by the steps of (1) reacting together (a) about 1 mole of maleic anhydride. (b) about 1 mole of styrene and (c) from about 1 to about 10 moles of a thiophene compound selected from the group consisting of thiophene of maleic anhydride, (b) about 1 mole of styrene and (c) fromabout I andalkyle-substituted thiophenes containing no substituent groups other than alkyl groups, at, a temperature of from about 75 C. to about 125 'C., and (2) esterifying the product thus obtained with a primary, normal, saturatedalcohol having from 14 to 16 carbon atoms.

8. As a new composition of matter, a reaction product prepared by the steps of (1) reacting "together-(a) about 1 mole of maleic anhydride, (byabfout 1 mole ofjsity'rerie and (0) from about- Ito about 10 moles of thiophene and'(2) esterifyr ing the product obtained in step (1) with a mixture of primary, normal, saturated alcohols having an average of about 14. carbon atoms per molecule. r

9. As a new composition of matter, a reaction product prepared by the'steps of (1) reacting together (a) about 1 mole of maleic anhydride,

(b) about 1 mole of styrene and (c) from about lrto about 10 moles of 2,5-di-tertiary-butyl thiophenejand (2) esterifying, the product obtained in step (1) with a mixture of primary, normal, saturated alcohols having an average of about 14 carbon atoms per molecule. 7

10. .As a new composition of matter, a reaction product prepared by the steps of 1) reacting together (a). about 1 mole of maleic anhydride, (2)) about 1' mole of styrene and (c) from about 1 to about 10 moles of 3-methyl thiophene and (2) esterifying the product obtained instep (1) with tetradecylalcohol.

" FERDINAND P. OTTO.

ORLAND M. VREIFF.

No references cited. 

1. AS A NEW COMPOSITION OF MATTER, A REACTION PRODUCT PREPARED BY THE STEPS OF (1) REACTING TOGETHER (A) ABOUT 1 MOLE OF MALEIC ANHYDRIDE, (B) ABOUT 1 MOLE OF STYRENE AND (C) FROM ABOUT 1 TO ABOUT 10 MOLES OF A THIOPHENE COMPOUND SELECTED FROM THE GROUP CONSISTING OF THIOPHENE AND ALKYL-SUBSTITUTED THIOPHENES CONTAINING NO SUBSTITUENT GROUPS OTHER THAN ALKYL GROUPS, AT A TEMPERATURE OF FROM ABOUT 75* C. TO ABOUT 125* C., AND (2) ESTERIFYING THE PRODUCT OBTAINED IN STEP (1) WITH A PRIMARY, NORMAL, SATURATED ALCOHOL HAVING FROM ABOUT 10 TO ABOUT 18 CARBON ATOMS. 